JP2007177166A - Water-soluble temper rolling liquid composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a water-soluble temper rolling liquid composition having excellent gum-up resistance and corrosion-protecting property. <P>SOLUTION: The water-soluble temper rolling liquid composition includes (A) 0.5-20 mass% (based on the composition) aromatic carboxylic acid expressed by general formula (1) (X)<SB>m</SB>-Ar-(COOH)<SB>n</SB>(X is NO<SB>2</SB>-, RO- or R- (R is a 1-10C hydrocarbon group); Ar is an aromatic hydrocarbon group having 2-4 bonds; and m and n are each an integer of 1 or 2; when m is 2, the multiple X groups may be the same or different), (B) 0.5-40 mass% aliphatic carboxylic acid having a carbon number of 8-24 and (C) at least one kind of basic compound selected from alkali metal hydroxides and alkanolamines in water. The molar ratio of the aliphatic carboxylic acid (B) to the aromatic carboxylic acid (A) (B/A) is 1.0-10. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to a tempered rolling fluid composition, and more particularly to a water-soluble tempered rolling fluid composition excellent in gum-up resistance, rust resistance, and the like.

  Temper rolling is performed at a small reduction after cold rolling, for the purpose of controlling the shape of the cold-rolled steel sheet, imparting mechanical properties (erasing the yield point elongation), adjusting gloss, etc. Has been done. The temper-rolled cold-rolled steel sheet is usually treated with a rust-preventing oil because there is a considerable period until it is processed and used in accordance with each application. However, the component in the water-soluble temper rolling agent used in the temper rolling step and the component in the rust preventive oil cause a chemical reaction, thereby producing a so-called “gum-up” adhesive. The sticking material embeds foreign matter such as iron powder and carbon and accumulates on the transport roll, which is transferred to the steel plate and remarkably impairs the surface quality, and also causes "slip" in subsequent press processing. May cause problems. Therefore, it is required to be a gum-up-resistant temper rolling agent that can prevent the occurrence of gum-up.

Further, after temper rolling, the cold-rolled steel sheet may be stored for a long time in a state where only the temper rolling solution is adhered, so that itself must be excellent in rust prevention. Furthermore, the tempered rolling liquid is required to have good degreasing properties and good rolling properties (specifically, for example, good wettability and an appropriate friction coefficient).
Furthermore, the water-soluble tempered rolling fluid is usually used after diluting the tempered rolling fluid with water about 10 to 50 times. However, the quality of the diluted water may be a problem. In other words, when water-soluble temper rolling agent is prepared using water with high hardness such as industrial water as dilution water, the dissolved or dispersed state of the compound in the temper rolling agent changes, and calcium and sodium replace fatty acid and soap. And scum may occur. The occurrence of such scum not only has an unfavorable appearance, but also may cause a problem in maintaining stable performance as a temper rolling agent.

Conventionally, as this type of water-soluble temper rolling agent, those mainly composed of alkanolamine salts of dibasic acids and aromatic carboxylic acids have been used. Specifically, for example, (a) dibasic A water-soluble tempered rolling oil mainly composed of a salt of an acid and the like with a primary alkanolamine and an inorganic alkali (see Patent Document 1), (b) a salt of spikrispolic acid, p-nitrobenzoic acid and the like with an alkanolamine Water-soluble tempered rolling oil containing water (see Patent Document 2), (c) Water-soluble tempered rolling oil mainly containing an aliphatic dibasic acid and a saturated fatty acid, a monoenecarboxylic acid, and an alkanolamine (Patent Document) 3), (d) a water-soluble preparation mainly containing a salt of alkanolamine such as benzothiazolylthioalkylenecarboxylic acid and aliphatic dicarboxylic acid or aromatic dicarboxylic acid. Rolling oil (see Patent Document 4), and the like.
However, all of these oil agents have insufficient gum-up resistance and are not necessarily sufficient in terms of rust prevention. Therefore, the actual situation is that it is not possible to obtain a temper rolled steel sheet having sufficient performance for any performance. Therefore, in the temper rolling industry, it is desired to develop an oil agent that has excellent performance in both the gum-up resistance and the rust resistance.
In addition, as described above, there is a demand for the appearance of an oil agent that does not generate scum even when industrial water having high hardness is used as dilution water for the oil agent.

JP-A-61-101600 JP-A-5-59389 JP-A-7-188690 JP 2000-87073 A

  Under such circumstances, the first object of the present invention is to provide a water-soluble tempered rolling liquid composition that is excellent in both the gum-up resistance and the rust-proof performance. Furthermore, the present invention is excellent in both the anti-gum resistance and anti-rust properties, and does not generate scum even when industrial water with high hardness is used as the dilution water, and is a water-soluble compound that can exhibit good performance. A second object is to provide a quality rolling liquid composition.

  The present inventors are a water-soluble tempered rolling liquid containing a specific aromatic carboxylic acid, a specific aliphatic carboxylic acid and a basic compound, and by adjusting the mixing ratio of each carboxylic acid to a specific range. And found that the purpose can be achieved. The present invention has been completed based on such findings.

That is, the present invention
1. In water, on a composition basis, (A) the following general formula (1)
(X) _m -Ar- (COOH) _n (1)
[Wherein, X is NO ₂ —, RO—, or R— (wherein R is a hydrocarbon group having 1 to 10 carbon atoms), Ar is an aromatic hydrocarbon group having 2 to 4 bonds, m and n each represent an integer of 1 or 2, and when m is 2, X may be the same or different. ]
0.5 to 20% by mass of an aromatic carboxylic acid represented by formula (B) 0.5 to 40% by mass of an aliphatic carboxylic acid having 8 to 24 carbon atoms, and (C) an alkali metal hydroxide and A water-soluble tempered rolling fluid composition containing at least one basic compound selected from alkanolamines, the content ratio of the aliphatic carboxylic acid (B) and the aromatic carboxylic acid (A), B / A (molar ratio) is 1.0 to 10 in water-soluble tempered rolling fluid composition,
2. The water-soluble tempered rolling liquid composition according to claim 1, wherein 70 mol% or more of the aliphatic carboxylic acid of (B) is an aliphatic monocarboxylic acid,
3. The water-soluble tempered rolling liquid composition according to claim 2, wherein 80 mol% or more of the aliphatic monocarboxylic acid (B) is an aliphatic monocarboxylic acid having a branched chain.
4). Content of the basic compound of (C) is more than the neutralization equivalent of (A) and (B) component, The water-soluble tempered rolling liquid composition in any one of Claims 1-3,
5. The water-soluble tempered rolling fluid composition according to any one of claims 1 to 4, wherein the aromatic carboxylic acid of (A) is nitrobenzoic acid and / or an alkoxybenzoic acid having 1 to 5 carbon atoms.
6). A water-soluble tempered rolling fluid composition obtained by diluting the water-soluble tempered rolling fluid composition according to any one of 1 to 5 with diluted water 10 to 50 times;
Is to provide.

  The water-soluble tempered rolling liquid composition in the first invention of the present invention is excellent in both performances of gum-up resistance and rust resistance. In addition, the water-soluble tempered rolling liquid composition of the second invention of the present invention is excellent in both performance of gum-up resistance and rust prevention, and even when water with high hardness is used as dilution water, Scum generation can be suppressed.

The first invention in the present invention satisfies the following conditions. That is, in water, on a composition basis, (A) the following general formula (1)
(X) _m -Ar- (COOH) _n (1)
[Wherein, X is NO _2- , RO-, or R- (where R is a hydrocarbon group having 1 to 10 carbon atoms), Ar is an aromatic hydrocarbon group having 2 to 4 bonds. , M and n represent an integer of 1 or 2, and when m is 2, X may be the same or different. ]
0.5 to 20% by mass of an aromatic carboxylic acid represented by formula (B) 0.5 to 40% by mass of an aliphatic carboxylic acid having 8 to 24 carbon atoms, and (C) an alkali metal hydroxide and A water-soluble tempered rolling fluid composition containing at least one basic compound selected from alkanolamines, the blending ratio of the aliphatic carboxylic acid (B) and the aromatic carboxylic acid (A), B / A (molar ratio) is a water-soluble tempered rolling fluid composition characterized by 1.0 to 10.

  In the general formula (1) of the component (A), the hydrocarbon group having 1 to 10 carbon atoms represented by R is preferably a linear or branched alkyl group or alkenyl group. Specific examples of preferable R include a methyl group, an ethyl group, an n-propyl group, an iso-propyl group, various (n-, sec-, tert-, and iso-) butyl groups, various pentyl groups, various hexyl groups, Examples thereof include various heptyl groups, various octyl groups, various nonyl groups, various decyl groups, and alkenyl groups corresponding to these alkyl groups (excluding methyl groups). R is preferably an alkyl group having 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms.

  As the aromatic hydrocarbon group having 2 to 4 bonds of Ar, any of benzoic acid residue, phthalic acid residue, isophthalic acid residue, terephthalic acid residue having 1 or 2 bonds in the aromatic ring Aromatic monocarboxylic acid residues and dicarboxylic acid residues such as benzoic acid residues and phthalic acid residues are particularly preferable because they are easily available.

  Preferable examples of the aromatic carboxylic acid represented by the general formula (1) include (di) nitrated products (meaning nitrated products or dinitrated products) and (di) alkoxy acids of benzoic acid or phthalic acid. (Alkyl group having 1 to 4 carbon atoms), (di) alkyl (alkyl group having 1 to 4 carbon atoms), alkyl (alkyl group having 1 to 4 carbon atoms) nitrate, alkoxy (alkyl group having 1 carbon atom) -4) nitrated compounds, alkoxy (alkyl group having 1 to 4 carbon atoms) alkyl (alkyl group having 1 to 4 carbon atoms) compound are preferable, specifically, p-nitrobenzoic acid, p-methoxybenzoic acid, p -Ethoxybenzoic acid, pn propoxybenzoic acid, p-isopropoxybenzoic acid, pn butoxybenzoic acid, p-sec butoxybenzoic acid, p-tertbutoxybenzoic acid, p-isobutoxy Benzoic acid, p-methylbenzoic acid, p-ethylbenzoic acid, pnpropylbenzoic acid, p-isopropylbenzoic acid, pnbutylbenzoic acid, p-secbutylbenzoic acid, p-tertbutylbenzoic acid P-isobutylbenzoic acid, 4-methyl 3-nitrobenzoic acid, 3-nitrophthalic acid, and the like.

  In this invention, these aromatic carboxylic acids are used individually by 1 type or in mixture of 2 or more types. The blending amount is 0.5 to 20% by mass, preferably 1 to 15% by mass based on the total amount of the composition. If the blending amount of the aromatic carboxylic acid is 0.5 to 20% by mass, it forms a salt with the basic compound (C) and has the effect of increasing the rust resistance of the composition, and is anti-gum-proof. Property can also be kept good.

  In the water-soluble tempered rolling liquid composition of the present invention, an aliphatic carboxylic acid having 8 to 24 carbon atoms, preferably 12 to 20 carbon atoms, is blended as the component (B). Examples of the aliphatic carboxylic acid having 8 to 24 carbon atoms include saturated or unsaturated aliphatic monocarboxylic acid and aliphatic dicarboxylic acid having a linear or branched chain.

  Specific examples of the aliphatic carboxylic acid having 8 to 24 carbon atoms include various octanoic acids, various nonanoic acids, various decanoic acids, various undecanoic acids, various dodecanoic acids, various tetradecanoic acids, various hexadecanoic acids, various octadecanoic acids, various Eicosanoic acid, aliphatic monocarboxylic acids such as various docosanoic acids, octanedioic acid (suberic acid), nonanedioic acid (azeleic acid), decanedioic acid (sebacic acid), dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, Aliphatic dicarboxylic acids such as octadecanedioic acid.

  As for the aliphatic carboxylic acid (B), 70 mol% or more is preferably an aliphatic monocarboxylic acid. If 70 mol% or more of the aliphatic carboxylic acid is an aliphatic monocarboxylic acid, the water-soluble tempered rolling liquid composition has the effect of improving the anti-rust property while maintaining good gum-up resistance. The proportion of the aliphatic monocarboxylic acid in the aliphatic carboxylic acid is more preferably 80 mol% or more, and even more preferably 90 mol% or more.

  In the present invention, these aliphatic carboxylic acids are used singly or in combination of two or more. The blending amount is 1 to 30% by mass, preferably 5 to 15% by mass, based on the total amount of the composition. When the content of the aliphatic carboxylic acid as the component (B) is 1% by mass or more, rust preventive properties are recognized, and when it is 30% by mass or less, the gum-up resistance and the like are not deteriorated.

  In the water-soluble tempered rolling liquid composition of the present invention, the blending ratio of the aliphatic carboxylic acid (B) and the aromatic carboxylic acid (A), B / A (molar ratio) is 1.0 to 1.0. 10 and preferably 1.0 to 8, particularly preferably 2.0 to 5.0. If the B / A (molar ratio) is less than 1.0, the gum-up property is insufficient. On the other hand, if the B / A (molar ratio) exceeds 10, the rust prevention performance may be lowered.

In the present invention, as the component (C), at least one basic compound selected from alkali metal hydroxides and alkanolamines is blended.
Examples of the alkali metal hydroxide include sodium hydroxide, potassium hydroxide, and lithium hydroxide. In addition, as alkanolamine, monoethanolamine, diethanolamine, triethanolamine, mono n-propanolamine, di (n-propanol) amine, tri (n-propanol) amine, monoisopropanolamine, diisopropanolamine, triisopropanolamine And methyl isopropanolamine. Among these alkanolamines, primary or secondary alkanolamines having 2 to 4 carbon atoms are preferable.

  In the present invention, it is necessary to contain at least one basic compound selected from the alkali metal hydroxide of component (C) and alkanolamine. The content of the component (C) is preferably at least the neutralization equivalent of the components (A) and (B). (C) If the content of at least one basic compound selected from the alkali metal hydroxides and alkanolamines of the component is not less than the neutralization equivalent of the components (A) and (B), (A) And each carboxylic acid of (B) forms a favorable salt with (C) component, and expresses the outstanding rust prevention property. The amount of component (C) is more preferably 1.0 to 1.2 equivalents of components (A) and (B).

  As the component (C) of the present invention, one or more basic compounds selected from the group consisting of the above alkali metal hydroxides and alkanolamines can be arbitrarily used. It is more preferable to mix one or more types with one or more types of alkanolamines. In this case, the mixing ratio is arbitrary, but from the viewpoint of gum-up resistance, it is preferable that the alkanolamine is in excess equivalent to the alkali metal hydroxide. For example, the alkanolamine is attached to 1 equivalent of the alkali metal hydroxide. It is more preferable that it is 1-8 equivalent, and also 1.5-5 equivalent.

  The water-soluble tempered rolling fluid composition of the present invention is a water-soluble tempered rolling fluid composition in which the components (A), (B), and (C) are blended with water. There is no restriction | limiting in particular about the water used here, For example, deionized water, a pure water, a tap water, industrial water etc. can be used, A deionized water and a pure water are preferable. Moreover, the content is 30-90 mass% normally on the basis of a water-soluble temper rolling liquid composition.

  The water-soluble tempered rolling liquid composition of the present invention has the above-described composition, but may further contain known additives as necessary. Examples of such additives include polyalkylene glycols such as polyethylene glycol and polypropylene glycol, alkylene oxide adducts such as ethylene oxide (EO) and propylene oxide (PO) of polyalkylene glycol, and water solubility such as methylcellulose. There is a polymer. Such a water-soluble polymer has an effect of suppressing the generation of sticky non-volatile content remaining on the roll of temper rolling (build-up resistance), and is usually based on a water-soluble temper rolling composition, About 0.5 to 15% by mass is blended.

  In addition, sodium salts and potassium salts of inorganic acids such as boric acid, tungstic acid, molybdic acid, phosphoric acid, carbonic acid, sulfuric acid, silicic acid, nitric acid, and nitrous acid; triazoles such as benzotriazole, methylbenzotriazole, tolyltriazole, and hydrocarbyltriazole And salts thereof; thiazoles such as mercaptobenzothiazole and salts thereof; fatty acid alkanolamides; imidazolines; oxazolines, and the like, water-soluble metal corrosion inhibitors such as rust-preventing action of a water-soluble tempered rolling liquid composition There is. Other examples include anionic surfactants such as sulfuric acid and sulfonic acid esters; nonionic surfactants such as polyoxyethylene compounds. The amount of additives such as these water-soluble metal corrosion inhibitors is usually in the range of 10% by mass or less based on the water-soluble tempered rolling fluid composition.

Although the water-soluble tempered rolling liquid composition of the present invention has the above-described configuration, the pH of the composition is preferably 7 to 10, and more preferably 8 to 9. If pH is 7-10, there exists an effect which keeps rust prevention property and wettability favorable.
Further, the water-soluble tempered rolling fluid composition of the present invention preferably has a friction coefficient lower than a certain value, for example, the friction coefficient is preferably 0.3 or less with a Kamata type friction tester, 0.2 The following are more preferable. If the friction coefficient is 0.3 or less, the temper rolling has a small fluctuation range of the rolling load, and has an effect of performing stable transfer of the roll surface.

  The water-soluble tempered rolling fluid composition of the present invention is a stock solution of a so-called water-soluble tempered rolling fluid, and is usually diluted 10 to 50 times with dilution water and used for actual temper rolling. In this case, deionized water, pure water, tap water, or the like can be used as dilution water.

The second invention in the present invention has the following configuration. In the first aspect of the invention, the water-soluble water in which 80 mol% or more, preferably 90 mol% or more, more preferably 95 mol% or more of the aliphatic monocarboxylic acid (B) is an aliphatic monocarboxylic acid having a branched chain. It is a tempered rolling liquid composition.
By having such a composition, in addition to having the performance of the first invention, even when industrial water with high hardness is used as dilution water, the occurrence of scum can be suppressed and the performance is reduced. I don't have to. Therefore, regardless of whether the dilution water is hard water or soft water, tap water, industrial water, ion exchange water, distilled water, and the like can be arbitrarily used.

EXAMPLES Next, although an Example demonstrates this invention in detail, this invention is not restrict | limited at all by these examples. The performance of the water-soluble tempered rolling liquid composition was evaluated according to the following method.
(1) Gum-up resistance 10 g of each water-soluble tempered rolling liquid composition sample and 70 g of commercially available rust preventive oil ("Dafney Oil Coat Z-3" manufactured by Idemitsu Kosan Co., Ltd.) are collected in a 300 ml container, It stirred at 1000 rpm for 16 hours at 70 degreeC. Thereafter, the container was washed with a hexane solvent, and the adhered matter after washing was weighed as a gum amount.

(2) Rust prevention test A steel plate (60 × 80 × 1 mm) specified in JIS G 3141 is degreased, immersed in a sample of each water-soluble tempered rolling liquid composition, dried, and then the test piece indoor exposure test and stack A test was conducted.
In the indoor exposure test, the presence and degree of rust and stain were observed after 10 days. In the stack test, the presence or absence and degree of rust and stain were observed after 10 days at a temperature of 50 ° C. and a humidity of 95% RH.
(3) Friction coefficient It measured using the Kamata pendulum type friction tester.

(4) Conditioning rolling experiment Rolling was performed under the following conditions using a four-stage small rolling mill, and the rolling load fluctuation range during rolling was measured.
・ Rolling conditions Roll diameter 135mm
Rolled material SPCC-SB (200m x 50mm x 0.05mm)
Rolling load 3.8kN (3.9tf)
Rolling rate 3%
Rolling speed 50 m / min.

Examples 1-5 and Comparative Examples 1-3
A water-soluble tempered rolling liquid composition was prepared using the components shown in Table 1. Various performances were evaluated for these prepared compositions and commercially available water-soluble tempered rolling oils. The results are shown in Table 1. In Table 1, the other components are a mixture of a water-soluble polymer (ethylene glycol EO, PO adduct), glycoether, nonionic surfactant and benzotriazole.

According to Table 1, the water-soluble tempered rolling liquid composition of Examples 1 to 5 having a B / A (molar ratio) of 1.0 or more is “no gum production” or “a small amount of gum production”. It can be seen that the gum-up resistance is excellent. On the other hand, Comparative Example 1 in which B / A (molar ratio) is 0.3 is “a large amount of gum generation”, while B / A (molar ratio) is ∞, that is, it does not contain an A component. Moreover, in Comparative Example 2 in which the monocarboxylic acid in B is 70 mol%, no gum is produced, but it is found that rust is generated in the rust prevention test.
In addition, (monocarboxylic acid having a branched chain) / (monocarboxylic acid) (mol%) in B
The water-soluble tempered rolling fluid compositions of Examples 2 to 5 with 100% do not generate scum even when diluted with industrial water, but in the case of Example 1 whose value is 72%, scum is generated. I know what to do.
Further, according to Table 1, the friction coefficients of Examples 1 to 3 and 5 are all 3 or less, but in Comparative Examples 1 and 4, the friction coefficient is high and 3 or more. Further, in Examples 2 and 3, the load fluctuation width in the temper rolling is small at 2.5 kN or less, whereas Comparative Example 3 is 3.9 kN, and the load fluctuation width in the temper rolling is large. The

  The water-soluble tempered rolling liquid composition of the present invention is a water-soluble tempered rolling liquid composition that is excellent in both performances of gum-up resistance and rust resistance. In addition, the water-soluble tempered rolling liquid composition of the present invention is excellent in both the anti-gum resistance and rust-proof performance, and suppresses the occurrence of scum even when water with high hardness is used as dilution water. It is useful as a water-soluble tempered rolling liquid composition.

Claims (6)

In water, on a composition basis, (A) the following general formula (1)
(X) _m -Ar- (COOH) _n (1)
[Wherein, X is NO ₂ —, RO—, or R— (wherein R is a hydrocarbon group having 1 to 10 carbon atoms), Ar is an aromatic hydrocarbon group having 2 to 4 bonds, m and n each represent an integer of 1 or 2, and when m is 2, X may be the same or different. ]
0.5 to 20% by mass of an aromatic carboxylic acid represented by formula (B) 0.5 to 40% by mass of an aliphatic carboxylic acid having 8 to 24 carbon atoms, and (C) an alkali metal hydroxide and A water-soluble tempered rolling fluid composition containing at least one basic compound selected from alkanolamines, the content ratio of the aliphatic carboxylic acid (B) and the aromatic carboxylic acid (A), B / A (molar ratio) is 1.0-10, The water-soluble refining rolling liquid composition characterized by the above-mentioned. The water-soluble tempered rolling liquid composition according to claim 1, wherein 70 mol% or more of the aliphatic carboxylic acid (B) is an aliphatic monocarboxylic acid. The water-soluble tempered rolling liquid composition according to claim 2, wherein 80 mol% or more of the aliphatic monocarboxylic acid (B) is an aliphatic monocarboxylic acid having a branched chain. Content of the basic compound of (C) is more than the neutralization equivalent of (A) and (B) component, The water-soluble refining rolling liquid composition in any one of Claims 1-3. The water-soluble tempered rolling liquid composition according to any one of claims 1 to 4, wherein the aromatic carboxylic acid (A) is nitrobenzoic acid and / or an alkoxybenzoic acid having 1 to 5 carbon atoms. A water-soluble tempered rolling fluid composition obtained by diluting the water-soluble tempered rolling fluid composition according to any one of claims 1 to 5 with diluted water 10 to 50 times.